More line narrowing in TROSY by decoupling of long-range couplings: shift correlation and JNC′ coupling constant measurements

Since the introduction of RDCs in high-resolution NMR studies of macromolecules, there is a growing interest in the development of accurate, and sensitive methods for determining coupling constants. Most methods for extracting these couplings are based on the measurement of the splitting between multiplet components in J-coupled spectra. However, these methods are often unreliable since undesired multiple-bond couplings can considerably broaden the multiplet components and consequently make accurate determination of their position difficult. To demonstrate one approach to this problem, G-BIRD^(r) decoupled TROSY sequences are proposed for the measurement of ¹J_NH and ¹J_NC′ coupling constants. Resolved or unresolved splittings due to remote protons are removed by a G-BIRD^(r) module employed during t₁ and as a result, spectra with narrow, well-resolved peaks are obtained from which heteronuclear one-bond couplings can be accurately measured. Moreover, introduction of a spin-state-selective α/β-filter in the TROSY sequence allows the separation of the ¹J_NC′ doublet components into two subspectra which contain the same number of peaks as the regular TROSY spectrum. The ¹J_NC′ couplings are obtained from the displacement between the corresponding peaks in the subspectra.     

Structure of odd–odd La at high spin

The high spin states in the N=79 odd–odd ¹³⁶La nucleus have been investigated by in-beam γ-spectroscopic techniques following the ¹³⁰Te(¹¹B, 5n)¹³⁶La reaction at E=52 MeV using an array, consisting of eight Compton-suppressed clover germanium detectors. Thirty nine new γ rays have been assigned to ¹³⁶La on the basis of γ ray singles and γγ-coincidence data. The level scheme of ¹³⁶La has been extended above the known 115 ms isomer upto an excitation energy of 4.6 MeV and spin 18. Thirty one new levels have been proposed and spin-parity assignments for most of the newly proposed levels have been made on the basis of the deduced asymmetry ratios and polarisation information for the de-exciting transitions. The observed positive parity yrast band has been compared with the theoretical calculation, done within the framework of particle rotor coupling model (PRM) where the two odd quasi-particles are coupled to an axially symmetric core. The level structure has been discussed in the light of the known systematics of the neighbouring N=79 isotonic nuclei.     

J Coupling between C and H across Hydrogen Bonds in Proteins

Two new two- or three-dimensional NMR methods for measuring ^3hJ_C′N and ^2hJ_C′H coupling constants across hydrogen bonds in proteins are presented. They are tailored to suit the size of the TROSY effect, i.e., the degree of interference between dipolar and chemical shift anisotropy relaxation mechanisms. The methods edit 2D or 3D spectra into two separate subspectra corresponding to the two possible spin states of the ¹H^N spin during evolution of ¹³CO coherences. This allows ^2hJ_C′H to be measured in an E.COSY-type way while ^3hJ_C′N can be measured in the so-called quantitative way provided a reference spectrum is also recorded. A demonstration of the new methods is shown for the ¹⁵N,¹³C-labeled protein chymotrypsin inhibitor 2.     

Formation of Fe i –B pairs in silicon at high temperatures

We report on the detection of Fe _i –B pairs in heavily B doped silicon using ⁵⁷Fe emission Mössbauer spectroscopy following implantation of radioactive ⁵⁷Mn⁺ parent ions (T _1/2?=?1.5 min) at elevated temperatures >?850 K. The Fe _i –B pairs are formed upon the dissociation of Fe _i –V pairs during the lifetime of the Mössbauer state (T _1/2?=?100 ns). The resulting free interstitial Fe_i diffuses over sufficiently large distances during the lifetime of the Mössbauer state to encounter a substitutional B impurity atom, forming Fe _i –B pairs, which are stable up to ～1,050 K on that time scale.     

Theoretical investigations of the spin Hamiltonian parameters for the CoCl(PPh3)3 molecules

The perturbation formulas of the spin Hamiltonian parameters (zero-field splitting and g factor g_// and g_⊥) are established for a 3d⁸ ion in trigonally distorted tetrahedra for the first time. In the theoretical treatments, the contributions from the Jahn–Teller effect, the ligand orbital and spin–orbit coupling interactions and configuration interactions are taken into account from the cluster approach in a uniform way. The above formulas are applied to the studies of the spin Hamiltonian parameters for the three CoCl(PPh₃)₃ molecules, and the experimental electron paramagnetic resonance spectra of all the molecules are satisfactorily explained. The significant compressions of the ligand tetrahedra with mixed chlorine and PPh₃ groups around Co⁺ are analysed for three distinct CoCl(PPh₃)₃ compounds, characterised by the Cl–Co–P bond angles θ larger than the tetrahedral angle of 109.47°. The local trigonal distortions are discussed in view of the Jahn–Teller effect.     

Sensitivity improvement and new acquisition scheme of heteronuclear active-coupling-pattern-tilting spectroscopy

A simplified phase-cycling scheme for heteronuclear active-coupling-pattern tilting (ACT) spectroscopy is presented. It is demonstrated that the theoretically expected twofold sensitivity gain over earlier implementations can be experimentally realized. A further intensity increase by a factor of 2 is obtained with standard sensitivity-enhancement pulse-sequence elements. The HSQC-HECADE sequence presented is designed for an accurate determination of heteronuclear one-bond and, with subsequent I-spin isotropic mixing, long-range coupling constants. As an exemplary application, the determination of the (3)J(N,Hbeta) coupling constants in a peptide at natural isotope abundance is demonstrated. Additionally, a new polarization-transfer step for the long-range HSQC-HECADE experiment is proposed which avoids a fixed delay tuned to a specific coupling-constant value. Thus, the long-range correlation experiment does not require prior knowledge of the coupling constants to be measured and yields more uniform cross-peak intensity for a broad range of active coupling constants.     

NQR, NMR and Crystal Structure Studies of [C(NH2)3]3Sb2Br9

The crystal structure of [C(NH₂)₃]₃Sb₂Br₉ was determined at 143 K: monoclinic, space group C2/c, Z = 4, a = 15.695 (3), b = 9.039(2), c = 18.364(3) Å, β = 96.94(1)°. The structure consists of two crystallographically independent guanidinium ions and two-dimensional corrugated sheets of (Sb₂Br₉ ^3?) _n , in which SbBr₆ octahedra are connected through three bridging Br atoms each other. One of the cations situates in a cavity of the (Sb₂Br₉ ^3?) _n layer with statistical disorder, while the other situates between the layers without disorder. Three ⁸¹Br NQR resonance lines were assignable to terminal Br atoms, while only one line was found for two inequivalent bridging Br atoms. All the ⁸¹Br NQR resonance lines were subjected to fade-out at low temperatures. The temperature dependence curve of ¹H NMR T ₁ showed well defined two minima, which were explained by postulating the C₃ reorientations of two types of cations with very different activation energies. The DTA (DSC) measurement revealed a phase transition of a first-order type at 444 K.     

The 2D {P} Spin-Echo-Difference Constant-Time [C, H]-HMQC Experiment for Simultaneous Determination of JH3′P and JC4′P in C-Labeled Nucleic Acids and Their Protein Complexes

A two-dimensional {³¹P} spin-echo-difference constant-time [¹³C, ¹H]-HMQC experiment (2D {³¹P}-sedct-[¹³C, ¹H]-HMQC) is introduced for measurements of ³J_C4′P and ³J_H3′P scalar couplings in large ¹³C-labeled nucleic acids and in DNA–protein complexes. This experiment makes use of the fact that ¹H–¹³C multiple-quantum coherences in macromolecules relax more slowly than the corresponding ¹³C single-quantum coherences. ³J_C4′P and ³J_H3′P are related via Karplus-type functions with the phosphodiester torsion angles β and ε, respectively, and their experimental assessment therefore contributes to further improved quality of NMR solution structures. Data are presented for a uniformly ¹³C, ¹⁵N-labeled 14-base-pair DNA duplex, both free in solution and in a 17-kDa protein–DNA complex.     

Solid-State Rb NMR Study in Powdered RbMnCl3

Structural phase transition at 290 K and the implication on the intermediate phase above 290 K in powdered RbMnCl₃ are observed by using a solid-state ⁸⁷Rb NMR spectroscopy. Quadrupole coupling constants (e²qQ/h), the asymmetry parameters (η), and the relative peak intensities for two physically nonequivalent Rb sites, Rb(I) and Rb(II), are determined from nonlinear least-squares fits to the ⁸⁷Rb NMR powder patterns in the temperature range from 260 to 330 K. Quadrupole coupling constants and the asymmetry parameters are examined for the detection of the phase transition resulting in a significant structural change in the Rb(II) site. In addition, changes in the relative peak intensity between the Rb(I) and Rb(II) sites seem to suggest the existence of an anomalous intermediate phase, which is complemented by the differential scanning calorimetry and X-ray diffraction studies.     

Simplified multiplet pattern HSQC-TOCSY experiment for accurate determination of long-range heteronuclear coupling constants

A new two-dimensional pulse sequence for accurately determining heteronuclear coupling constants is presented. It is derived from HSQC and HECADE techniques with B0 gradient coherence selection. The main feature of the proposed method is spectra with only one component of the IS doublet; i.e., the final result is equivalent to a selective broadband excitation of either Salpha or Sbeta spin states and a preservation of these states during the entire experiment. The effect is obtained by an appropriate combination of in- and antiphase coherences. It is demonstrated that heteronuclear single-bond as well as long-range coupling constants and their relative signs are readily evaluated. The proposed sequence is equally or less sensitive to a variation of heteronuclear one-bond couplings than previously published, closely related sequences. The new method is applied to a peptide sample for determination of 3JN, Hbeta.     

Theoretical study on the reactions of CH3NHNH2 with ground state O(3P) atom and excited state O(1D) atom

The reaction mechanisms of methylhydrazine (CH₃NHNH₂) with O(³P) and O(¹D) atoms have been explored theoretically at the MPW1K/6-311+G(d,p), MP2/6-311+G(d,p), MCG3-MPWPW91 (single-point), and CCSD(T)/cc-pVTZ (single-point) levels. The triplet potential energy surface for the reaction of CH₃NHNH₂ with O(³P) includes seven stable isomers and eight transition states. When the O(³P) atom approaches CH₃NHNH₂, the heavy atoms, namely N and C atoms, are the favourable combining points. O(³P) atom attacking the middle-N atom in CH₃NHNH₂ results in the formation of an energy-rich isomer (CH₃NHONH₂) followed by migration of O(³P) atom from middle-N atom to middle-H atom leading to the product P6 (CH₃NNH₂+OH), which is one of the most favourable routes. The estimated major product CH₃NNH₂ is consistent with the experimental measurements. Reaction of O(¹D) + CH₃NHNH₂ presents different features as compared with O(³P) + CH₃NHNH₂. O(¹D) atom will first insert into C–H2, N1–H4, and N2–H5 bonds barrierlessly to form the three adducts, respectively. There are two most favourable paths for O(¹D) + CH₃NHNH₂. One is that the C–N bond cleavage accompanied by a concerted H shift from O atom to N atom (mid-N) leads to the product P_I (CH₂O + NH₂NH₂), and the other is that the N–N bond rupture along with a concerted H shift from O to N (end-N) forms P_IV (CH₃NH₂ + HNO). The similarities and discrepancies between two reactions are discussed.     

Sensitivity- and Gradient-Enhanced Hetero (ω1) Half-Filtered TOCSY Experiment for Measuring Long-Range Heteronuclear Coupling Constants

An enhanced version of the X(ω₁) half-filtered TOCSY experiment for measurement of long-range heteronuclear coupling constants is proposed which yields high-quality spectra with substantially increased sensitivity and resolution. The modified method features gradient-enhanced X filtering sequences, broadband homonuclear decoupling duringt₁, optional¹J_XHscaling in theF₁domain, and gradient coherence selection in combination with the sensitivity-enhanced protocol for the TOCSY transfer. These modifications extend the applicability of the method—coupling constants can be measured accurately for natural abundance samples at low concentrations and for compounds yielding complex spectra. Computer-aided analysis of E.COSY-type multiplets is applied for the determination of heteronuclear long-range coupling constants.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Japanese efforts on coated conductor processing and its power applications: New 5 year project for materials and power applications of coated conductors (M-PACC)

Five years of Japanese national project (FY2003–FY2007) was ended last spring with remarkable success. The national project was originally aimed for development of coated conductors which have high superconductivity performance and long length enough to fabricate high temperature superconducting (HTS) electric power devices. Preliminary research and development of HTS electric power devices were carried out as well. A series of R&D results will be summarized and reviewed in this paper.The new 5 years Japanese national project has started last June (FY2008–FY2012) to develop HTS electric power applications including SMES, cables and transformers and to develop/produce coated conductors satisfying the requirements from the respective power devices. Collaborative R&D efforts by national laboratories, universities and private companies have been started with the supports of NEDO and METI.The accomplishment of the previous project will be summarized and the plans and goals of the new project will be presented in this paper.     

Paracharge phenomenology: systematics of the new hadrons

A systematic semiquantitative account of all aspects of the strong and electromagnetic interactions of all the newly discovered hadronic states (theψ’s, theχ’s, etc.) is presented within the framework of the paracharge scheme. Extensions of ideas familiar from the SU₃ classification scheme to SU₄ are shown to provide an understanding of the new states seen in the decays ofψ (3.1) andψ′ (3.7), including their masses and gross decay characteristics. The decays ofψ (3.1) andψ′ (3.7) themselves are studied in some detail. Since these are of electromagnetic origin in the scheme, their electromagnetic mixing with the resonance at 4.15 GeV (theP-state of the scheme) is important. Once this is taken into account, the resulting picture is in excellent agreement with available data.     

Cross-sections for the formation of isomeric pair Ge through (n, 2n), (n, p) and (n, α) reactions measured over 13.73 MeV to 14.77 MeV and calculated from near threshold to 20 MeV neutron energies

The cross-sections for formation of isomeric pair, ⁷⁵Ge^m(σ_m) and ⁷⁵Ge^g(σ_g), through ⁷⁶Ge(n, 2n), ⁷⁵As(n, p) and ⁷⁸Se(n, α) reactions were measured at 13.73 MeV, 14.42 MeV and 14.77 MeV neutrons and also estimated using EMPIRE-II and TALYS codes over neutron energies from near threshold to 20 MeV. For each (n, 2n), (n, p) and (n, α) reaction, the cross-section initially increases with neutron energy, but starts decreasing as the neutron energy exceeds the respective threshold of (n, 3n), (n, pn) and (n, αn) reactions. The higher values of σ_m relative to σ_g reveal that the transitions of the excited ⁷⁵Ge from higher energy levels to metastable state (7⁺/2) are favored as compared to unstable ground state (1⁻/2). The present values of cross sections for formation of ⁷⁵Ge^m,g through (n, 2n) and (n, α) reactions are lower, and that of (n, p) reaction are higher compared to most of the corresponding literature cross-sections.     

Al Chemical Shielding Anisotropy

Accurate values for the²⁷Al chemical shielding anisotropy (CSA) are reported for sapphire (α-Al₂O₃). The values (δ_σ= −17.3 ± 0.6 ppm, η_σ= 0.03 ± 0.06) are obtained from single-crystal²⁷Al NMR and appear to be the first convincing determination of an²⁷Al CSA.     

182Os核yrast带结构SU(3)→U(5)→SU(3)形状相变的有序性研究

对于发生在同一个原子核中的转动诱导发生基准态结构的量子相变,可以理解为一种从高有序激发模式向着低有序激发模式的演化：被布居到高角动量态的高有序激发核,以E2跃迁的方式先行退耦到yrast带,再退耦到共存区(或临界点)时释放了有序的结构能,诱发价核子对耦合强度改变,重新组合出低有序的激发模式基准态,实现了基准态结构的过渡.对核量子相变的这种描述,与朗道经典热相变理论之间有了某些相似的术语和物理内涵.本文把这种理解推广到了相继的二次相变中.以¹⁸²Os 核为例作了说明,并展 关键词： 量子相变 基态结构演化 F_max方案')" href="#">微观sdIBM-F_max方案 182Os核')" href="#">¹⁸²Os核     

The (γ,p) reaction in Au

Proton energy spectra of the ¹⁹⁷Au(e,p) reaction were measured in the region between 17 and 30 MeV at three angles: 40°, 90° and 140°. Two prominent bumps were observed in the (γ,p) spectra converted using virtual photon theory. The higher-energy bump shifts with photon energies and the lower-energy one stays at 10.5 MeV. The higher-energy bump is much larger at 40° than at 140°; on the contrary the angular dependence of the lower-energy bump is small. Neither bump can be described by a statistical calculation. A calculation of a microscopic shell model shows that the lower-energy bump is attributed to the decay of proton-particle–neutron-hole pairs in the T_> states, leaving a neutron hole around the Fermi surface. The higher-energy bump can be ascribed to the direct–semidirect mechanism. This paper gives the solution to a part of the long-standing question about the origin of photo-proton emission in heavy nuclei.     

Supercycled SW(f)-TPPM sequence for heteronuclear dipolar decoupling in solid-state nuclear magnetic resonance

The performance of a supercycled SW(f)-TPPM sequence for heteronuclear dipolar decoupling in solid-state NMR is analyzed here. The decoupling performance of this sequence with respect to experimental parameters, such as, the phase angle, proton offset and MAS frequency is studied. A comparison is made with two other commonly used decoupling schemes in solid-state NMR namely, SPINAL-64 and SW(f)-TPPM, on a sample of U-13C-labeled tyrosine. Our results show that supercycled SW(f)-TPPM performs better than the former sequences. Also, numerical spin dynamics studies are presented which support the experimentally observed efficiency in the decoupling.